CN102117908A - Non-aqueous electrolytic secondary battery and positive electrode for non-aqueous electrolytic secondary battery - Google Patents
Non-aqueous electrolytic secondary battery and positive electrode for non-aqueous electrolytic secondary battery Download PDFInfo
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- CN102117908A CN102117908A CN2011100090729A CN201110009072A CN102117908A CN 102117908 A CN102117908 A CN 102117908A CN 2011100090729 A CN2011100090729 A CN 2011100090729A CN 201110009072 A CN201110009072 A CN 201110009072A CN 102117908 A CN102117908 A CN 102117908A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
Primary objective of the invention is to provide a nonaqueous electrolytic secondary battery and a positive electrode for a nonaqueous electrolytic secondary battery. The positive electrode includes a positive electrode active material layer containing a positive electrode active material and a coupling agent represented by a general formula (1). The positive electrode active material includes lithium transition metal oxide particles. At least one rare-earth compound selected from the rare-earth compound group consisting of specific rare-earth hydroxides and specific rare-earth oxyhydroxides is fixed on the surfaces of the lithium transition metal oxide particles in a dispersed form.
Description
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery and positive electrode for nonaqueous electrolyte secondary battery, relate in particular to improved rechargeable nonaqueous electrolytic battery of characteristic and positive electrode for nonaqueous electrolyte secondary battery after the trickle charge.
Background technology
In recent years, the small-sized and lightweight of mobile phone, notebook computer, personal digital assistant personal digital assistant devices such as (PDA, Personal Digital Assistant) develops just rapidly, requires as the battery of its driving power high capacity more.Follow to discharge and recharge by lithium ion and between positive and negative electrode, move the lithium ion battery that discharges and recharges,, therefore be widely used as the driving power of personal digital assistant device as described above owing to have high-energy-density, high power capacity.
Here, above-mentioned personal digital assistant device exists to consume the higher trend of electric power along with the function of animation regeneration function, game function and so on enriches, and expects further high capacity strongly.For with above-mentioned rechargeable nonaqueous electrolytic battery high capacity, except the countermeasure of the capacity that improves active material, increase the countermeasures such as loading of active material of per unit volume, improve the countermeasure of the charging voltage of battery in addition.Yet, improve under the situation of charging voltage of battery, the problem that exists electrolyte to decompose easily, particularly at high temperature preserve or the situation of trickle charge under, can produce following problem: electrolyte decomposition and produce gas is big thereby the internal pressure of cell expansion or battery becomes.Consider these problems, proposed scheme shown below.
Proposed to use the battery of following substances: Li
1-xM
1-yL
yO
2In the shown lithium composite xoide, L uses the element be selected from the group that rare earth element, IIIb family element and IVb family element formed, and with coupling agent it is handled, and makes the not residual binding groups inactivation with the lithium composite xoide bonding.And put down in writing thus and can realize that cycle characteristics improves (with reference to following patent documentation 1) under the situation of intermittent cyclic repeatedly under the hot environment to a certain degree.
In addition, for reach with above-mentioned patent documentation 1 in the record the identical purpose of purpose, following battery: Li has been proposed
1-xM
1-yL
yO
2In the shown lithium composite xoide, L uses the element be selected from the group that rare earth element, IIIb family element and IVb family element formed, and the active material skin section contains at least a kind of element Le that is selected from the group that Al, Mn, Ti, Mg, Zr, Nb, Mo, W and Y form, and with coupling agent aforementioned active material has been carried out surface treatment (with reference to following patent documentation 2).
And then, proposed to contain the battery that aluminium is coupling agent in the anode mixture etc., and put down in writing and can improve anodal adaptation thus and realize that cycle characteristics improves (with reference to following patent documentation 3).
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-242303 communique
Patent documentation 2: TOHKEMY 2007-18874 communique
Patent documentation 3: Japanese kokai publication hei 9-199112 communique
Summary of the invention
The problem that invention will solve
Yet, in the technology of above-mentioned patent documentation 1 and patent documentation 3 records,, therefore do not form stable epithelium on the surface of positive active material just because of contain coupling agent in the positive pole.In addition, in the technology of above-mentioned patent documentation 2 records, contain coupling agent in the positive pole, and the surface adhering of positive active material has the compound that contains elements such as Al, but owing to heat-treat under high temperature (for example, 650 ℃) behind this compound of adhesion, so Elements Diffusion such as Al is to positive active material, even be present in the surface, be that form with oxide exists, so the surface of positive active material does not still form stable epithelium yet.Owing to these reasons, in the above-mentioned prior art, the problem that the characteristic when having the raising that especially can't realize the preservation characteristics under the high temperature, trickle charge improves.
Therefore, main purpose of the present invention is to provide a kind of rechargeable nonaqueous electrolytic battery and positive electrode for nonaqueous electrolyte secondary battery, even this rechargeable nonaqueous electrolytic battery is at high temperature preserved, trickle charge, capacity descends also few, and gas produces also few.
The scheme that is used to deal with problems
In order to achieve the above object, the present invention is a kind of positive electrode for nonaqueous electrolyte secondary battery, it has the positive electrode active material layer that contains positive active material, the particle that possesses the lithium-containing transition metal oxide that contains nickel and/or cobalt in the above-mentioned positive active material, it is characterized in that, be selected from by erbium hydroxide, the hydroxyl oxidize erbium, ytterbium hydroxide, the hydroxyl oxidize ytterbium, terbium hydroxide, the hydroxyl oxidize terbium, dysprosium hydroxide, the hydroxyl oxidize dysprosium, holmium hydroxide, the hydroxyl oxidize holmium, thulium hydroxide, the hydroxyl oxidize thulium, the hydroxide lutetium, the hydroxyl oxidize lutetium, water acidifying neodymium, the hydroxyl oxidize neodymium, samaric hydroxide, the hydroxyl oxidize samarium, praseodymium hydroxide, europium hydroxide, the hydroxyl oxidize europium, gadolinium hydroxide, the hydroxyl oxidize gadolinium, lanthanum hydroxide, the hydroxyl oxidize lanthanum, yttrium hydroxide, the hydroxyl oxidize yttrium, scandium hydroxide, at least a kind of rare earth compound in the rare earth compound group that the hydroxyl oxidize scandium is formed adheres to the surface of the particle of above-mentioned lithium-containing transition metal oxide with the state that disperses, and above-mentioned positive electrode active material layer contains the coupling agent shown in the general formula (1).
(M is A1, and R1, R2 represent alkyl or the alkoxyl of carbon number below 18 respectively independently.R1 and R2 can be identical, also can be different.Alkyl and alkoxyl can be in straight chain shape, the chain any one.N is the integer below 3.N is under 2 or 3 the situation, a plurality of R1 of existence and R2 can distinguish identical also can be different.Also can bonded functional group on the M.)
As above-mentioned formation, contain the coupling agent (aluminum coupling agent) shown in the general formula (1) at positive electrode active material layer, and be selected from least a kind of rare earth compound in the rare earth compound group of forming by the oxyhydroxide of the hydroxide of terres rares and terres rares (below, sometimes abbreviate rare earth compound as) adhere to the state that disperses lithium-containing transition metal oxide particle the surface (promptly, even the rare earth element of rare earth compound diffuses in the positive active material or the surface that is present in the particle of lithium-containing transition metal oxide can not exist with the form of the oxide of terres rares yet), then above-mentioned coupling agent optionally carries out coordination with the rare earth compound on the surface of the particle that adheres to lithium-containing transition metal oxide.Thus, can around terres rares, form stable epithelium, and, by with the interaction of rare earth compound, the characteristic that catalytic electrolysis liquid is decomposed descends and suppresses the decomposition of electrolyte significantly.Thus, trickle charge gas produces also less, capacity descends also little battery even can obtain to carry out.
Here, above-mentioned rare earth compound group preferably is made up of erbium hydroxide, hydroxyl oxidize erbium, lanthanum hydroxide and hydroxyl oxidize lanthanum.
As rare earth compound, when using erbium hydroxide or hydroxyl oxidize erbium, can further bring into play above-mentioned action effect, when using lanthanum hydroxide or hydroxyl oxidize lanthanum,, therefore can reduce anodal manufacturing cost because lanthanum is cheap.
The average grain diameter of above-mentioned rare earth compound is preferably more than the 1nm and below the 100nm.
Stipulate shown in the reasons are as follows of average grain diameter of the aforesaid particle that forms by rare earth compound.That is, reason is that when this average grain diameter surpassed 100nm, the particle diameter of rare earth compound was excessive with respect to the lithium-transition metal composite oxide particle grain size, so the surface of lithium-transition metal composite oxide particle can not covered densely by rare earth compound.Therefore, the lithium-transition metal composite oxide particle becomes big with the area that nonaqueous electrolyte or its reduction decomposition product directly contact, and causes the oxidation Decomposition of nonaqueous electrolyte or its reduction decomposition product to increase, and charge-discharge characteristic descends.On the other hand, during less than above-mentioned 1nm, the surface of lithium-transition metal composite oxide particle is by coverings too densely such as terres rares hydroxide, and therefore in the lip-deep lithium ion occlusion of lithium-transition metal composite oxide particle, the decreased performance of emitting, charge-discharge characteristic descends.Consider above-mentioned reason, the average grain diameter of rare earth compound is more preferably more than the 10nm and below the 50nm.
Coupling agent shown in the above-mentioned general formula (1) is preferably at least a kind that is selected from the group of being made up of two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium (aluminum bis (ethylacetoacetate) mono (acetylacetonate)), ethyl acetoacetic ester diisopropyl ester aluminium ((Ethyl Acetoacetate) aluminium Diisopropoxide), three (ethyl acetoacetic ester) aluminium (aluminum tris (Ethyl Acetoacetate)).
This be because, when coupling agent is these materials, can further bring into play above-mentioned action effect.
A kind of rechargeable nonaqueous electrolytic battery, it is by the positive pole that possesses the positive active material particle, negative pole, barrier film and nonaqueous electrolytic solution are disposed in the shell body and form, described positive active material particle has the lithium-containing transition metal oxide of nickeliferous and/or cobalt, this rechargeable nonaqueous electrolytic battery is characterised in that, be selected from by erbium hydroxide, the hydroxyl oxidize erbium, ytterbium hydroxide, the hydroxyl oxidize ytterbium, terbium hydroxide, the hydroxyl oxidize terbium, dysprosium hydroxide, the hydroxyl oxidize dysprosium, holmium hydroxide, the hydroxyl oxidize holmium, thulium hydroxide, the hydroxyl oxidize thulium, the hydroxide lutetium, the hydroxyl oxidize lutetium, neodymium hydroxide, the hydroxyl oxidize neodymium, samaric hydroxide, the hydroxyl oxidize samarium, praseodymium hydroxide, europium hydroxide, the hydroxyl oxidize europium, gadolinium hydroxide, the hydroxyl oxidize gadolinium, lanthanum hydroxide, the hydroxyl oxidize lanthanum, yttrium hydroxide, the hydroxyl oxidize yttrium, scandium hydroxide, at least a kind of rare earth compound in the rare earth compound group that the hydroxyl oxidize scandium is formed adheres to the surface of the particle of above-mentioned lithium-containing transition metal oxide with the state that disperses, and disposes the coupling agent shown in the following general formula (1) in the above-mentioned shell body.
(M is A1, and R1, R2 represent alkyl or the alkoxyl of carbon number below 18 respectively independently.R1 and R2 can be identical, also can be different.Alkyl and alkoxyl can be in straight chain shape, the chain any one.N is the integer below 3.N is under 2 or 3 the situation, a plurality of R1 of existence and R2 can distinguish identical also can be different.Also can bonded functional group on the M.)
As mentioned above, coupling agent may not be included in the positive pole, as long as be disposed in the shell body (inside battery).For example, can be included in the electrolyte, in addition, also can contain other members of coupling agent in the inside battery configuration.But, when positive pole contains coupling agent, can successfully generate good epithelium on the surface of lithium-containing transition metal oxide particle, therefore more preferably contain coupling agent at positive pole.
Other business
(1) as the coupling agent that uses among the present invention, being not limited to above-mentioned substance, also can be (aluminum trisacetylacetate) such as single isopropoxy list oil oxygen base ethyl acetoacetic ester aluminium (aluminium monoisopropoxy monooleoxyethylacetoacetate), triacetyl acetic acid esters aluminium.In addition, in R1, R2 in the general formula of above-mentioned 5 kinds of coupling agents (1) and the general formula (1) can with the functional group (except that other functional groups R1, the R2) of M Direct Bonding shown in following table 1.
[table 1]
Alkoxyl in addition,, is not limited to the functional group shown in the above-mentioned table 1, so long as then can be any functional group as above-mentioned other functional groups 1,2.
When (2) containing coupling agent in the positive pole, the addition of coupling agent is preferably more than the 0.03 quality % with respect to the total amount of positive active material and below the 1.5 quality %.During less than 0.03 quality %, the amount of coupling agent is very few, can't fully suppress the decomposition reaction of electrolyte sometimes.On the other hand, when surpassing 1.5 quality %, the amount of coupling agent is excessive, for example contains in positive active material under the situation of cobalt also and the cobalt coordination, excessively forms epithelium, guiding discharge decreased performance as a result.Consider such reason, the addition of coupling agent is more preferably more than the 0.1 quality % and below the 0.6 quality %, more preferably more than the 0.2 quality % and below the 0.4 quality %.
(3) as the method that makes when containing coupling agent in the positive pole, the method that is mixed into when being applied to the positive active material slurry on the aluminium foil in the slurry is arranged, maybe will form positive plate behind the positive electrode active material layer and be impregnated into and remove the method for desolvating etc. in the solution that contains coupling agent then.
(4) particulate of rare-earth element compound is adhered to its surperficial positive active material with the state that disperses and can obtains by the manufacture method that comprises following operation: for example, in the solution that is dispersed with the positive active material particle, the hydroxide of rare earth element is separated out, and make this hydroxide be adhered to the surface of positive active material particle.Particularly, water soluble salts such as the nitrate by in the suspension that is dispersed with the positive active material particle, adding rare earth element, sulfate, and then add alkaline aqueous solutions such as NaOH, potassium hydroxide, the pH value of suspension is adjusted to for example 6～13 scope, thereby the hydroxide of rare earth element is separated out.
(5) after the hydroxide that makes rare earth element as mentioned above is adhered to the surface of positive active material particle, heat-treat usually.Heat treated temperature as this moment is preferably more than 80 ℃ and the scope below 500 ℃ usually, especially preferably more than 80 ℃ and the scope below 400 ℃.
When heat treated temperature was higher than 500 ℃, rare earth compound was present in the surface of positive active material particle with the form of oxide, and the spread of particles of part rare earth compound that adheres to the surface is to the inside of active material.Cause the efficiency for charge-discharge at initial stage to descend thus.And then rare earth compound does not exist with the form of hydroxide or oxyhydroxide, and exists with the form of oxide, so coupling agent can't be optionally and the rare earth compound coordination, can't form stable epithelium.In addition, about the concrete heat treatment temperature of each rare earth compound, explanation in following (6).
(6) as the rare earth compound that adheres to the surface of positive active material particle, as long as use the hydroxide or the oxyhydroxide of erbium, ytterbium, terbium, dysprosium, holmium, thulium, lutetium, neodymium, samarium, praseodymium, europium, gadolinium, lanthanum and yttrium etc.Concrete heat treatment temperature when here, the positive active material particle of the hydroxide of separating out above-mentioned each terres rares being heat-treated is carried out following explanation.
Erbium hydroxide
Under the situation of erbium hydroxide, erbium hydroxide decomposes and the temperature that is varied to the hydroxyl oxidize erbium is about 230 ℃, and this hydroxyl oxidize erbium further decomposes and the temperature that is varied to erbium oxide is about 440 ℃.And if the temperature that the positive active material particle of separating out erbium hydroxide is heat-treated reaches more than 440 ℃, then erbium hydroxide is varied to erbium oxide, and erbium diffuses to the inside of positive active material particle.If this kind formation then is difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out erbium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 440 ℃.
Ytterbium hydroxide
Under the situation of ytterbium hydroxide, with 5 ℃/minute speed rising heat treatment temperatures and carried out thermogravimetric analysis, the result confirms the flex point of weight change when about 230 ℃ and about 400 ℃, in the time of about 500 ℃ the variation of weight diminish, stable.Think this be because, ytterbium hydroxide begins decomposition and is varied to the hydroxyl oxidize ytterbium under about 230 ℃ temperature, and then this hydroxyl oxidize ytterbium begins further to decompose and is varied to ytterbium oxide under about 400 ℃ of temperature, and ytterbium hydroxide has been varied to ytterbium oxide under about 500 ℃ temperature.
Therefore, if the temperature that the positive active material particle of separating out ytterbium hydroxide is heat-treated is more than 400 ℃, then the hydroxyl oxidize ytterbium begins to be varied to ytterbium oxide, if more than 500 ℃, then ytterbium hydroxide is varied to ytterbium oxide, and ytterbium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out ytterbium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 500 ℃, preferably less than 400 ℃.
Terbium hydroxide
Under the situation of terbium hydroxide, terbium hydroxide decomposes and the temperature that is varied to the hydroxyl oxidize terbium is about 295 ℃, and this hydroxyl oxidize terbium further decomposes and the temperature that is varied to terbium oxide is about 395 ℃.And if the temperature that the positive active material particle of separating out terbium hydroxide is heat-treated is that then terbium hydroxide is varied to terbium oxide more than 395 ℃, and terbium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out terbium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 395 ℃.
Dysprosium hydroxide
Under the situation of dysprosium hydroxide, dysprosium hydroxide decomposes and the temperature that is varied to the hydroxyl oxidize dysprosium is about 275 ℃, and the hydroxyl oxidize dysprosium further decomposes and the temperature that is varied to dysprosia is about 450 ℃.
And if the temperature that the positive active material particle of separating out dysprosium hydroxide is heat-treated is that then dysprosium hydroxide is varied to dysprosia more than 450 ℃, and dysprosium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out dysprosium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 450 ℃.
Holmium hydroxide
Under the situation of holmium hydroxide, holmium hydroxide decomposes and the temperature that is varied to the hydroxyl oxidize holmium is about 265 ℃, and this hydroxyl oxidize holmium further decomposes and the temperature that is varied to holimium oxide is about 445 ℃.
Then, if the temperature that the positive active material particle of separating out holmium hydroxide is heat-treated is that then holmium hydroxide is varied to holimium oxide more than 445 ℃, and holmium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out holmium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 445 ℃.
Thulium hydroxide
Under the situation of thulium hydroxide, thulium hydroxide decomposes and the temperature that is varied to the hydroxyl oxidize thulium is about 250 ℃, and this hydroxyl oxidize thulium further decomposes and the temperature that is varied to thulium oxide is about 405 ℃.
And if the temperature that the positive active material particle of separating out thulium hydroxide is heat-treated is that then thulium hydroxide is varied to thulium oxide more than 405 ℃, and thulium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out thulium hydroxide is heat-treated, preferably heat treatment temperature is defined as less than 405 ℃.
The hydroxide lutetium
Under the situation of hydroxide lutetium, carried out thermogravimetric analysis, the result is that the hydroxide lutetium decomposes and the temperature that becomes the hydroxyl oxidize lutetium is about 280 ℃, and this hydroxyl oxidize lutetium further decomposes and the temperature that is varied to luteium oxide is about 405 ℃.
And if the temperature that the positive active material particle of separating out the hydroxide lutetium is heat-treated is more than 405 ℃, then the hydroxide lutetium is varied to luteium oxide, and lutetium diffuses to the inside of positive active material particle.In this case, be difficult to fully suppress the reaction of positive active material and nonaqueous electrolytic solution, and the charge-discharge characteristic of positive active material descends greatly.
Therefore, when the positive active material particle of separating out the hydroxide lutetium is heat-treated, preferably heat treatment temperature is defined as less than 405 ℃.
Neodymium hydroxide
Under the situation of neodymium hydroxide, neodymium hydroxide is varied to the hydroxyl oxidize neodymium under 335 ℃～350 ℃ temperature, is varied to neodymia under 440 ℃～485 ℃ temperature.
And the temperature of heat-treating as if the positive active material particle of the surface being separated out neodymium hydroxide is that then neodymium hydroxide is varied to neodymia more than 440 ℃, and neodymium diffuses to the inside of positive active material particle.In this case, same effect when neodymia can not get with neodymium hydroxide or hydroxyl oxidize neodymium, the characteristic of positive active material descends, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that neodymium hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 440 ℃.
Samaric hydroxide
Under the situation of samaric hydroxide, samaric hydroxide is varied to the hydroxyl oxidize samarium under 290 ℃～330 ℃ temperature, is varied to samarium oxide under 430 ℃～480 ℃ temperature.
And the temperature of heat-treating as if the positive active material particle of the surface being separated out samaric hydroxide is that then samaric hydroxide is varied to samarium oxide more than 430 ℃, and samarium diffuses to the inside of positive active material particle.In this case, same effect when samarium oxide can not get with samaric hydroxide or hydroxyl oxidize samarium, the characteristic of positive active material descends, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that samaric hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 430 ℃.
Praseodymium hydroxide
Under the situation of praseodymium hydroxide, make the surface of positive active material particle separate out praseodymium hydroxide after, remove moisture in passing thereby preferably heat-treat.Here, when the positive active material particle that praseodymium hydroxide is separated out on the surface is heat-treated,, can not get the effect same with praseodymium hydroxide if heat treated temperature is that about then praseodymium hydroxide is varied to oxide more than 310 ℃.
Therefore, when the positive active material particle that praseodymium hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 310 ℃.
Europium hydroxide
Under the situation of europium hydroxide, europium hydroxide is varied to the hydroxyl oxidize europium under about 305 ℃ temperature, be varied to europium oxide under about 470 ℃ temperature.
And the temperature of heat-treating as if the positive active material particle of the surface being separated out europium hydroxide is that then europium hydroxide is varied to europium oxide more than 470 ℃, and europium diffuses to the inside of positive active material particle.In this case, same effect when europium oxide can not get with europium hydroxide or hydroxyl oxidize europium, the characteristic of positive active material descends, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that europium hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 470 ℃.
Gadolinium hydroxide
Under the situation of gadolinium hydroxide, gadolinium hydroxide is varied to the hydroxyl oxidize gadolinium under 218 ℃～270 ℃ temperature, is varied to gadolinium oxide under 420 ℃～500 ℃ temperature.
And when the positive active material particle that gadolinium hydroxide is separated out on the surface was heat-treated, if heat treated temperature is that then gadolinium hydroxide is varied to gadolinium oxide more than 420 ℃, and gadolinium diffused to the inside of positive active material particle.In this case, same effect when gadolinium oxide can not get with gadolinium hydroxide or hydroxyl oxidize gadolinium, the characteristic of positive active material descends, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that gadolinium hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 420 ℃.
Lanthanum hydroxide
Under the situation of lanthanum hydroxide, lanthanum hydroxide is varied to the hydroxyl oxidize lanthanum under 310 ℃～365 ℃ temperature, and the hydroxyl oxidize lanthanum is varied to lanthana under 460 ℃～510 ℃ temperature.And, the temperature of heat-treating as if the positive active material particle of the surface being separated out lanthanum hydroxide is more than 600 ℃, then lanthanum hydroxide is varied to lanthana, same effect when can not get with lanthanum hydroxide or hydroxyl oxidize lanthanum, and lanthanum diffuses to the inside of positive active material particle and causes the characteristic of positive active material to descend, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that lanthanum hydroxide is separated out on the surface is heat-treated, preferably heat treatment temperature is defined as less than 460 ℃.
Yttrium hydroxide
Under the situation of yttrium hydroxide, yttrium hydroxide is varied to the hydroxyl oxidize yttrium under about 260 ℃ temperature, be varied to yittrium oxide under about 450 ℃ temperature.And, the temperature of heat-treating as if the positive active material particle of the surface being separated out yttrium hydroxide is more than 450 ℃, then yttrium hydroxide is varied to yittrium oxide, same effect when can not get with yttrium hydroxide or hydroxyl oxidize yttrium, and yttrium diffuses to the inside of positive active material particle and causes the characteristic of positive active material to descend, and characteristics such as efficiency for charge-discharge descend.
Therefore, when the positive active material particle that yttrium hydroxide is separated out on the surface is heat-treated, preferably make heat treatment temperature less than 450 ℃.
Here, for easy understanding, the hydroxide of above-mentioned terres rares is varied to the temperature of oxyhydroxide of terres rares and the temperature that is varied to the oxide of terres rares and is recorded in the following table 2.
[table 2]
| The kind of the hydroxide of terres rares | Be varied to the temperature of oxyhydroxide | Be varied to the temperature of oxide |
| Erbium hydroxide | About 230 ℃ | About 440 ℃ |
| Ytterbium hydroxide | About 230 ℃ | About 400 ℃ |
| Terbium hydroxide | About 295 ℃ | About 395 ℃ |
| Dysprosium hydroxide | About 275 ℃ | About 450 ℃ |
| Holmium hydroxide | About 265 ℃ | About 445 ℃ |
| Thulium hydroxide | About 250 ℃ | About 405 ℃ |
| The hydroxide lutetium | About 280 ℃ | About 405 ℃ |
| Neodymium hydroxide | 335～350℃ | 440～485℃ |
| Samaric hydroxide | 290～330℃ | 430～480℃ |
| Praseodymium hydroxide | - | About 310 ℃ |
| Europium hydroxide | About 305 ℃ | About 470 ℃ |
| Gadolinium hydroxide | 218～270℃ | 420～500℃ |
| Lanthanum hydroxide | 310～365℃ | 460～510℃ |
| Yttrium hydroxide | About 260 ℃ | About 450 ℃ |
In addition, except that above-claimed cpd, can also use the hydroxide or the oxyhydroxide of scandium.
(7) rare-earth element compound, is preferably more than the 0.005 quality % and below the 0.5 quality % in the value that rare earth element converts with respect to the adhesion amount of the total amount of positive active material.When the adhesion amount of rare-earth element compound is less than 0.005 quality %, the adhesion amount is very few, sometimes can't substantially improve the flash-over characteristic after the trickle charge, on the other hand, when the adhesion amount of rare-earth element compound surpasses 0.5 quality %, the particulate that the positive active material surface is not participated in discharging and recharging the rare earth compound of reaction excessively covers, so flash-over characteristic descends.Consider such reason, rare-earth element compound with respect to the adhesion amount of the total amount of positive active material more preferably more than the 0.01 quality % and the scope below the 0.3 quality %.
(8), can list the lithium-containing transition metal composite oxides of transition metal such as containing cobalt, nickel, manganese as the positive active material among the present invention.Particularly, be cobalt acid lithium, the lithium composite xoide of Ni-Co-Mn, the lithium composite xoide of Ni-Mn-Al, the composite oxides of Ni-Co-Al.In addition, these positive active materials can be used alone, but also also mix together.
(9) among the present invention used negative electrode active material so long as can then be not particularly limited as the material of the negative electrode active material of rechargeable nonaqueous electrolytic battery.As negative electrode active material, for example can list raw material of wood-charcoal material, tin oxide, lithium metal, silicon etc. such as graphite, coke can with the metal of lithium alloyage and their alloy etc.
(10) used nonaqueous electrolytic solution among the present invention as long as can be used in rechargeable nonaqueous electrolytic battery, then is not particularly limited.Usually, can list the nonaqueous electrolytic solution that contains support salt and solvent.As above-mentioned support salt, for example can list LiBF
4, LiPF
6, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiPF
6-x(C
nF
2n+1)
x[wherein, 1＜x＜6, n=1 or 2] etc.They can separately or mix use more than 2 kinds.Support the concentration of salt to be not particularly limited, preferably the scope that rises at 0.8～1.5mol/.As above-mentioned solvent, preferably use carbonic ester series solvents such as ethylene carbonate, propylene carbonate, gamma-butyrolacton, carbonic acid two ethyls, methyl ethyl carbonate, dimethyl carbonate, or a part of hydrogen of these solvents is replaced the carbonic ester series solvent that forms by F.As solvent, preferably cyclic carbonate and linear carbonate are used in combination.
The effect of invention
According to the present invention, can bring into play the effect of following excellence: even at high temperature preserve or trickle charge, capacity descends also few, and gas produces also few.
Description of drawings
Fig. 1 is the front elevation of the test cell in the embodiment.
Fig. 2 is the profile of observing along the A-A line direction of arrow of Fig. 1.
Fig. 3 is the key diagram that is used to measure cell thickness.
Fig. 4 is the photo when observing positive active material of the present invention by scanning electron microscope (SEM).
Fig. 5 is the photo when observing positive active material when adhering to rare earth compound by dry process by scanning electron microscope (SEM).
Description of reference numerals
1: positive pole
2: negative pole
3: barrier film
4: anodal collector plate
5: the negative pole collector plate
6: aluminium lamination wafer housings body
Embodiment
Below, the present invention is described in more detail according to embodiment, but the present invention is not subjected to any qualification of following examples, can suitably be changed in the scope that does not change its purport and implement.
(anodal making)
(1) utilize damp process to carry out the coating of hydroxyl oxidize erbium
With respectively with the 1.5mol% solid solution Mg and Al and the cobalt acid lithium 1000g that contains the Zr of 0.05mol% add in 1.5 liters the pure water and stir, after preparation is dispersed with the suspension of cobalt acid lithium, in this suspension, be added in dissolving 3.18g erbium nitrate pentahydrate in the pure water of 200mL and the solution that obtains.At this moment, for the pH value of the solution that will be dispersed with cobalt acid lithium is adjusted to 9, suitably add the sodium hydrate aqueous solution of 10 quality %.Then, after the interpolation of erbium nitrate pentahydrate solution finishes, suction filtration, so that after washing, resulting powder is dry under 120 ℃, obtain the powder of erbium hydroxide being arranged surperficial evenly adhesion of above-mentioned cobalt acid lithium.Then, with the heat treatment 5 hours in air under 300 ℃ of the powder that obtains.When heat-treating under 300 ℃ like this, whole or most erbium hydroxide is varied to the hydroxyl oxidize erbium, so the hydroxyl oxidize erbium adheres on the surface of positive active material particle with the state that disperses.Therefore but part is residual with the state of erbium hydroxide sometimes, and the situation that has erbium hydroxide on the surface of positive active material particle is also arranged.
(SEM) observes resulting positive active material by scanning electron microscope, the result confirms the following erbium compound (hydroxyl oxidize erbium) of average grain diameter 100nm evenly adheres to positive active material with homodisperse state surface as shown in Figure 4.In addition, in order to contrast, the positive active material SEM photo when Fig. 5 shows and mixes with erbium oxide by dry process.In this case, the erbium oxide particle that confirms average grain diameter 300～400nm is only attached to the recess of positive active material particle, do not have when adhering by damp process erbium compound below the average grain diameter 100nm adhere to the state that disperses.
In addition, measured the adhesion amount of erbium compound by ICP, the result in er element, is 0.12 quality % with respect to cobalt acid lithium.
(2) Zheng Ji making
With the above-mentioned positive active material that obtains, as carbon black (acetylene black) powder of the average grain diameter 30nm of anodal conductive agent and as the Kynoar (PVdF) of anodal adhesive with 95: 2.5: 2.5 ratio of mass ratio mixing after, will two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium in wherein being added in the N-N-methyl-2-2-pyrrolidone N-be adjusted into 50 quality % and the solution that obtains, further mixing and prepared the positive active material slurry.Then, this anode mixture slurry is applied to two sides as the aluminium foil of positive electrode collector, rolls after the drying, thereby made positive pole.In addition, the packed density of positive active material is 3.60g/cc.In addition, the content of above-mentioned two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium is 0.15 quality % with respect to the total amount of positive active material and conductive agent and PVdF.
The making of negative pole
In the aqueous solution, carbon material (graphite), CMC (sodium carboxymethylcellulose) and SBR (butadiene-styrene rubber) mixed with 98: 1: 1 mass ratio and prepared the negative electrode active material slurry, then this negative electrode active material slurry is applied to the two sides of Copper Foil, and then the calendering of dry back, made negative pole.In addition, the packed density of negative electrode active material is 1.75g/cc.
The preparation of nonaqueous electrolytic solution
For the solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) are formed with 3: 7 mixed of volume ratio, with 1 mol dissolving phosphorus hexafluoride acid lithium (LiPF
6), prepared nonaqueous electrolytic solution.
The making of battery
Lead terminal is installed respectively on above-mentioned both positive and negative polarity, at their two interpolars configurations barrier film and after being wound into helical form, is extracted the volume core and made spiral helicine electrode body, and then this electrode body is flattened, obtain the electrode body of platypelloid type.Then, the electrode body and the above-mentioned electrolyte of this platypelloid type is inserted in the shell body of aluminium lamination compressing tablet system, has made rechargeable nonaqueous electrolytic battery.In addition, this secondary cell is of a size of 3.6mm * 35mm * 62mm, and in addition, the design capacity with this secondary cell charge during to 4.40V is 780mAh.
As shown in Figures 1 and 2, the concrete structure of above-mentioned rechargeable nonaqueous electrolytic battery 11 is as follows.Anodal 1 with negative pole 2 across barrier film 3 and relative configuration, contain in the electrode body of the platypelloid type that constitutes by above-mentioned positive and negative polarities 1,2 and barrier film 3 and be soaked with nonaqueous electrolytic solution.Be connected with the negative pole collector plate with anodal collector plate 4 respectively with negative pole 2 above-mentioned anodal 1, formed the structure that to charge and to discharge as secondary cell.In addition, electrode body is configured in the accommodation space of the aluminium lamination wafer housings body 6 that possesses peristome 7 that is heat-sealed between the periphery.
Embodiment
(the 1st embodiment)
(embodiment 1)
Use the battery shown in the above-mentioned embodiment.
Below the battery that will make like this is called battery A1 of the present invention.
(embodiment 2)
Heat treatment temperature in making embodiment 1 is 120 ℃, to make battery similarly to Example 1.In addition, if heat treatment temperature is 120 ℃, then erbium hydroxide is not varied to the hydroxyl oxidize erbium, so erbium hydroxide adheres to the surface of positive active material particle with the state that disperses.
Below the battery that will make like this is called battery A2 of the present invention.
(comparative example 1)
In the positive active material slurry, do not add the coupling agent, similarly make battery with the foregoing description 1.
Below the battery that will make like this is called comparison battery Z1.
(comparative example 2)
Except the positive active material slurry does not add coupling agent, similarly make battery with the foregoing description 2.
Below the battery that will make like this is called comparison battery Z2.
(comparative example 3)
Except heat treatment temperature being changed to 600 ℃, make battery similarly to Example 1.In addition, if heat treatment temperature is 600 ℃, then erbium hydroxide is varied to erbium oxide, so erbium oxide adheres to the surface of positive active material particle.Below the battery that will make like this is called comparison battery Z3.
(comparative example 4)
In the positive active material slurry, do not add the coupling agent, similarly make battery with above-mentioned comparative example 3.Below the battery that will make like this is called comparison battery Z4.
(comparative example 5)
Except use zirconyl nitrate dihydrate 1.91g replaces the erbium nitrate pentahydrate, make battery similarly to Example 2.In addition, owing to the zirconium amount with respect to cobalt acid lithium is the molal quantity identical with the erbium amount of embodiment 2, therefore count 0.065 quality % with zr element.
Below the battery that will make like this is called comparison battery Z5.
(comparative example 6)
In the positive active material slurry, do not add the coupling agent, similarly make battery with above-mentioned comparative example 5.Below the battery that will make like this is called comparison battery Z6.
(comparative example 7)
Except use zirconyl nitrate dihydrate 1.91g replaces the erbium nitrate pentahydrate, make battery similarly to Example 1.In addition, owing to the zirconium amount with respect to cobalt acid lithium is the molal quantity identical with the erbium amount of embodiment 1, therefore count 0.065 quality % with zr element.
Below the battery that will make like this is called comparison battery Z7.
(comparative example 8)
In the positive active material slurry, do not add the coupling agent, similarly make battery with above-mentioned comparative example 7.
Below the battery that will make like this is called comparison battery Z8.
(experiment)
Under following condition, above-mentioned battery A1 of the present invention, A2 and comparison battery Z1～Z8 are discharged and recharged, investigated initial charge, residual capacity and swell increment, with their table 3 that the results are shown in.
Discharge and recharge condition
The charge condition of the 1st circulation
Carry out constant current charge to cell voltage with the electric current of 1C (750mA) and reach 4.40V, and then carry out constant-potential charge to current value with the voltage of 4.40V and reach 37.5mA.
The discharging condition of the 1st circulation
Carrying out constant current with the electric current of 1C (750mA) is discharged to cell voltage and reaches 2.75V.
End
Termination between above-mentioned charging and the discharge is spaced apart 10 minutes.
The mensuration of initial charge
Carry out 1 charge and discharge cycles test under the condition above-mentioned discharging and recharging, measure initial stage discharge capacity Qo and initial stage charging capacity Q1, by the initial charge shown in these solid measures following (1) formula.
Initial charge=(initial stage discharge capacity Qo/ initial stage charging capacity Q1) * 100 (%) ... (1)
(60 ℃ of trickle charge)
Carry out the test of 1 charge and discharge cycles with the 1C multiplying power, measure discharge capacity Q2 (the discharge capacity Q2 before the trickle charge test) once more after, in 60 ℃ thermostat, placed one hour.Then, keep 60 ℃ environment to reach 4.40V, again with the constant-potential charge of 4.40V 64 hours with constant current charge to the cell voltage of 750mA.
(mensuration of the swell increment of battery)
As shown in Figure 3, with two faces of the maximum area of 2 flat board 12 clamping batteries 11.After the discharge of the 1st circulation and charge and discharge cycles test back measure the distance (cell thickness) of 12 of these 2 flat boards.With the cell thickness after the discharge of the 1st circulation is L1 (below, abbreviate cell thickness L1 as), is L2 (below, abbreviate cell thickness L2 as) with the cell thickness after the charge and discharge cycles test.Then, calculate the swell increment shown in following (2) formula by these thickness.
Swell increment=cell thickness L2-cell thickness L1 ... (2)
(mensuration of residual capacity rate)
After measuring swell increment, be cooled to room temperature, at room temperature measure the 1st discharge capacity Q3 after trickle charge is tested then, obtain the residual capacity rate by following (3) formula.
Residual capacity rate=(the discharge capacity Q2 before the 1st the discharge capacity Q3/ trickle charge test after the trickle charge test) * 100 (%) ... (3)
[table 3]
Add under the situation of coupling agent, the kind of coupling agent all is two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium.
Can confirm by table 3, have as the hydroxide of the erbium of terres rares or oxyhydroxide and contain battery A1 of the present invention, the A2 of coupling agent in the surface adhering of positive active material particle, initial charge and residual capacity rate height, and cell expansion is inhibited.
Relative therewith, confirm that surface adhering at the positive active material particle has the hydroxide of erbium or oxyhydroxide but the comparison battery Z1, the Z2 that do not contain coupling agent, owing to do not contain coupling agent, therefore the periphery at the hydroxide of erbium etc. does not form stable epithelium, consequently, the residual capacity rate is low, and cell expansion becomes big.
In addition, confirm: have among comparison battery Z5, the Z6 of hydroxide of the zirconium that is not terres rares in the surface adhering of positive active material particle, the residual capacity rate is all lower, and cell expansion becomes big.For the comparison battery Z6 that does not contain coupling agent, its reason is identical with the above-mentioned relatively reason shown in the battery Z1.In addition, for the comparison battery Z5 that contains coupling agent, think that its reason is, do not suppress the catalytic action of nickel, cobalt during for zirconium, so electrolyte decomposes still.
And then confirming at the material of surface adhering is among the comparison battery Z3, Z4, Z7, Z8 of the oxide of erbium or zirconium, no matter whether contain coupling agent, initial charge and residual capacity rate are all low, and cell expansion becomes big.Under the situation of the oxide of erbium, zirconium, think that because heat treatment temperature is high a part of erbium, zirconium diffuse to the inside of positive active material particle, so initial charge descends.In addition, under the situation of the oxide of erbium, zirconium, think that coupling agent is not adhered to the periphery of this oxide, but only adhere to partly on the part cobalt acid lithium that therefore adhesion and the coupling agent on surface can't interact, the residual capacity rate is low, and cell expansion becomes greatly.
(the 2nd embodiment)
(embodiment)
Except using 3.06g lanthanum nitrate hexahydrate to replace the erbium nitrate pentahydrate, similarly make battery with the embodiment 1 of aforementioned the 1st embodiment.In addition, be the molal quantity identical with respect to the lanthanum amount of cobalt acid lithium, so count 0.098 quality % with lanthanum element with the erbium amount of embodiment 1.
Below the battery that will make like this is called battery B of the present invention.
(comparative example)
In the positive active material slurry, do not add the coupling agent, similarly make battery with the embodiment of above-mentioned the 2nd embodiment.
Below the battery that will make like this is called comparison battery Y.
(experiment)
With the same condition of the condition shown in the experiment of aforementioned the 1st embodiment under above-mentioned battery B of the present invention and comparison battery Y are discharged and recharged, by having investigated the swell increment of initial charge, residual capacity and battery, with the results are shown in the table 4 of they with the same method of the method shown in the experiment of aforementioned the 1st embodiment.
[table 4]
The kind of coupling agent is two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium.
Can confirm that by above-mentioned table 4 surface adhering of positive active material particle has as the oxyhydroxide of the lanthanum of terres rares and contains the battery B of the present invention of coupling agent, compare with the comparison battery Y that does not contain coupling agent, residual capacity rate height, cell expansion is inhibited.Think that the reason shown in the experiment of its reason and aforementioned the 1st embodiment is identical.
(the 3rd embodiment)
(embodiment 1)
As coupling agent, replace two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium, and use ethyl acetoacetic ester diisopropyl ester aluminium, the embodiment 1 with aforementioned the 1st embodiment similarly makes battery in addition.
Below the battery that will make like this is called battery C1 of the present invention.
(embodiment 2)
As coupling agent, replace two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium, and use three (ethyl acetoacetic ester) aluminium, the embodiment 1 with aforementioned the 1st embodiment similarly makes battery in addition.
Below the battery that will make like this is called battery C2 of the present invention.
(experiment)
To above-mentioned battery C1 of the present invention, C2, with the same condition of the condition shown in the experiment of aforementioned the 1st embodiment under discharge and recharge, by having investigated the swell increment of initial charge, residual capacity and battery, with the results are shown in the table 5 of they with the same method of the method shown in the experiment of aforementioned the 1st embodiment.
[table 5]
Compound 1: ethyl acetoacetic ester diisopropyl ester aluminium
2: three (ethyl acetoacetic ester) aluminium of compound
Can confirm that by above-mentioned table 5 used battery C1 of the present invention, the C2 of ethyl acetoacetic ester diisopropyl ester aluminium or three (ethyl acetoacetic ester) aluminium, initial charge and residual capacity rate are all high, and cell expansion is inhibited.
Utilizability on the industry
The present invention can be applied to personal digital assistant devices such as mobile phone, notebook computer, PDA driving power, particularly need in the purposes of high power capacity. In addition, can also expect to carry out in the height output purposes that requires Continuous Drive at high temperature, and in the harsh purposes of the working environment of the battery of HEV, electric tool and so on.
Claims (5)
1. positive electrode for nonaqueous electrolyte secondary battery, this positive electrode for nonaqueous electrolyte secondary battery has the positive electrode active material layer that contains positive active material, possess the particle of the lithium-containing transition metal oxide that contains nickel and/or cobalt in the described positive active material, it is characterized in that
Be selected from by erbium hydroxide, the hydroxyl oxidize erbium, ytterbium hydroxide, the hydroxyl oxidize ytterbium, terbium hydroxide, the hydroxyl oxidize terbium, dysprosium hydroxide, the hydroxyl oxidize dysprosium, holmium hydroxide, the hydroxyl oxidize holmium, thulium hydroxide, the hydroxyl oxidize thulium, the hydroxide lutetium, the hydroxyl oxidize lutetium, neodymium hydroxide, the hydroxyl oxidize neodymium, samaric hydroxide, the hydroxyl oxidize samarium, praseodymium hydroxide, europium hydroxide, the hydroxyl oxidize europium, gadolinium hydroxide, the hydroxyl oxidize gadolinium, lanthanum hydroxide, the hydroxyl oxidize lanthanum, yttrium hydroxide, the hydroxyl oxidize yttrium, scandium hydroxide, at least a kind of rare earth compound in the rare earth compound group that the hydroxyl oxidize scandium is formed adheres to the surface of the particle of described lithium-containing transition metal oxide with the state that disperses, and described positive electrode active material layer contains the coupling agent shown in the general formula (1)
M is A1, R1, R2 represent alkyl or the alkoxyl of carbon number below 18 respectively independently, R1 and R2 can be the same or different, alkyl and alkoxyl can be in straight chain shape, the chain any one, n is the integer below 3, n is under 2 or 3 the situation, a plurality of R1 of existence and R2 can distinguish identical also can be different, also can bonded functional group on the M.
2. positive electrode for nonaqueous electrolyte secondary battery according to claim 1, described rare earth compound group is made up of erbium hydroxide, hydroxyl oxidize erbium, lanthanum hydroxide and hydroxyl oxidize lanthanum.
3. positive electrode for nonaqueous electrolyte secondary battery according to claim 1 and 2, the average grain diameter of described rare earth compound are more than the 1nm and below the 100nm.
4. according to each described positive electrode for nonaqueous electrolyte secondary battery in the claim 1～3, the coupling agent shown in the described general formula (1) is for being selected from least a kind in the group of being made up of two (ethyl acetoacetic ester) single acetyl acetic acid esters aluminium, ethyl acetoacetic ester diisopropyl ester aluminium, three (ethyl acetoacetic ester) aluminium.
5. rechargeable nonaqueous electrolytic battery, it is disposed in the shell body by the positive pole that possesses the positive active material particle, negative pole, barrier film and nonaqueous electrolytic solution and forms, described positive active material particle has the lithium-containing transition metal oxide of nickeliferous and/or cobalt, this rechargeable nonaqueous electrolytic battery is characterised in that
Be selected from by erbium hydroxide, the hydroxyl oxidize erbium, ytterbium hydroxide, the hydroxyl oxidize ytterbium, terbium hydroxide, the hydroxyl oxidize terbium, dysprosium hydroxide, the hydroxyl oxidize dysprosium, holmium hydroxide, the hydroxyl oxidize holmium, thulium hydroxide, the hydroxyl oxidize thulium, the hydroxide lutetium, the hydroxyl oxidize lutetium, neodymium hydroxide, the hydroxyl oxidize neodymium, samaric hydroxide, the hydroxyl oxidize samarium, praseodymium hydroxide, europium hydroxide, the hydroxyl oxidize europium, gadolinium hydroxide, the hydroxyl oxidize gadolinium, lanthanum hydroxide, the hydroxyl oxidize lanthanum, yttrium hydroxide, the hydroxyl oxidize yttrium, scandium hydroxide, at least a kind of rare earth compound in the rare earth compound group that the hydroxyl oxidize scandium is formed adheres to the surface of the particle of described lithium-containing transition metal oxide with the state that disperses, and described shell body contains the coupling agent shown in the following general formula (1)
M is A1, R1, R2 represent alkyl or the alkoxyl of carbon number below 18 respectively independently, R1 and R2 can be the same or different, alkyl and alkoxyl can be in straight chain shape, the chain any one, n is the integer below 3, n is under 2 or 3 the situation, a plurality of R1 of existence and R2 can distinguish identical also can be different, also can bonded functional group on the M.
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| JP2010001322A JP5675113B2 (en) | 2010-01-06 | 2010-01-06 | Nonaqueous electrolyte secondary battery and positive electrode for nonaqueous electrolyte secondary battery |
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| CN107112527A (en) * | 2014-12-25 | 2017-08-29 | 三洋电机株式会社 | Positive active material and rechargeable nonaqueous electrolytic battery |
| CN107112527B (en) * | 2014-12-25 | 2020-03-03 | 三洋电机株式会社 | Positive electrode active material and nonaqueous electrolyte secondary battery |
| CN114068864A (en) * | 2021-11-15 | 2022-02-18 | 宁德新能源科技有限公司 | Negative pole piece and electrochemical device and electronic equipment comprising same |
| CN114068864B (en) * | 2021-11-15 | 2023-04-11 | 宁德新能源科技有限公司 | Negative pole piece and electrochemical device and electronic equipment comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5675113B2 (en) | 2015-02-25 |
| JP2011141989A (en) | 2011-07-21 |
| US8822076B2 (en) | 2014-09-02 |
| CN102117908B (en) | 2014-11-05 |
| US20110165453A1 (en) | 2011-07-07 |
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